Water-soluble quaternary amine containing monoazo dyestuffs

ABSTRACT

WATER-SOLUBLE BASIC MONOAZO DYESTUFFS WHICH ARE SUITABLE FOR THE DYEING OR PRINTING OF TEXTILE FIBROUS MATERIALS CONSISTING OF NATIVE OR REGENERATIVE CELLULLSE, POLYAMIDES, POLYESTERS, POLYACRYLONITRILE OR POLYVINYLIDENE CYANIDE.

United States Patent US. Cl. 260-149 Claims ABSTRACT OF THE DISCLOSUREWater-soluble basic monoazo dyestuffs which are suitable for the dyeingor printing of textile fibrous materials consisting of native orregenerative cellulose, polyamides, polyesters, polyacrylonitrile orpolyvinylidene cyanide.

The present invention provides basic azo dyestuffs and a process forpreparing them.

We have found that basic azo dyestufis which are free from sulfonic acidand carboxylic acid groups and which corresponding to the generalFormula I in which Y represents hydrogen or halogen, alkyl, alkoxy,trifiuoromethyl, nitro, alkyl-sulfone, aryl-sulfone, cyano, or acarboxylic acid ester group, a sulfonic acid amide group which may besubstituted, a carboxylic acid amide group which may be substituted, oracyl group, Z represents hydrogen, a non-water-solubilizing substituent,R represents hydrogen, an alkyl or aryl radical which may besubstituted, a cycloalkyl or an aralkyl radical, R represents hydrogen,an alkyl radical which may be substituted, a cycloalkyl or an aralkylradical, or R and R together with the nitrogen atom represent aheterocyclic group, A represents a phenylene or naphthylene radicalwhich may be substituted, R R and R represent lower alkyl groups whichmay be substituted, and X represents an anion, can be prepared and theyhave valuable properties. The novel dyestutfs may be obtained in such amanner that (a) the diazonium compound of a quaternary amine of thegeneral Formula 11 in which Y, Z, R R R and X have the meaning givenabove, is coupled with a coupling component of the Formula III (III) inwhich A, R, and R have the meaning given above, or

ice

(b) an azo dyestuff to the general Formula IV in which Y, X, R R R R andA have the meanings given above, is reacted with a quaternating agentwhich introduces into the dyestuii" molecule the radical R and the anionX The method (a) is especially suitable and generally applicable. Thequaternary amines of the Formula II used in this method can be obtainedby quaternating an amine of the Formula V with an agent which introducesinto the dyestuff molecule the radical R and the anion X andsubsequently splitting off the acyl group according to the usualmethods, for example by means of inorganic acids.

As quaternating agents, there may be used alkyl halides, aralkylhalides, halogeno-acetamides, B-halogeno-propionitriles,halogeno-hydrins, alkyl esters of sulfuric acid or alkyl esters oforganic sulfonic acids. Suitable quaternating agents are, for example,methyl chloride, methyl bromide or methyl iodide, ethyl bromide or ethyliodide, propyl bromide or propyl iodide, benzyl chloride, dimethylsulfate, diethyl sulfate, benzene-sulfonic acid methyl ester orp-toluene-sulfonic acid methyl-, ethyl-, propyl, or butyl ester.Quaternization is carried out in Water or in an inert organic solvent,for example, in a hydrocarbon, chlorohydrocarbon or nitro-hydrocarbon,for example, benzene, toluene, xylene, tetrachloroethane, chloroform,carbon tetrachloride, monoor dichlorobenzene or nitrobenzene, in an acidamide or acid anhydride, for example, dimethylformamide,N-methyl-acetamide, or acetic acid anhydride, in dimethyl sulfoxide orin a ketone, for example, acetone or methylethylketone. Instead of anorganic solvent, there may also be used an excess of the quaternatingagent. Quaternization may be effected at an elevated temperature, ifdesired under pressure. The conditions which are the most favorable ineach case can easily be determined in a preliminary test.

Suitable compounds fo the Formula V are l-acylamino-Z-N,N-dialkylamino-benzenes which may carry in the henzene nucleus nofurther substituents or the substituents Y and Z; Y representing ahalogen atom, such as chlorine or bromine, an alkyl, alkoxy,trifluoromethyl, nitro, alkylsulfone, aryl-suifone, cyano, or acarboxylic acid ester group, or a sulfonic acid amide group which may besubstituted, a carboxylic acid amide group which may be substituted oran acyl group and Z representing a non-watersolubilizing substituentsuch as a halogen atom, and alkyl, alkoxy, alkyl-sulfone, aryl-sulfone,sulfamyl, carbamyl, aryl, aryloxy, acylamino, carbalkoxy,trifiuoromethyl, cyano or acyl group.

Diazotization of the amines of the Formula II is effected according tomethods known per se, for example, by means of hydrochloric acid andsodium nitrite.

Coupling with the coupling components of the Formula III is effected bya method known per se, for example, in a neutral or acid medium, ifdesired or necessary in the presence of a buffer compound or a compoundwhich accelerates coupling, such, for example, as pyridine.

As coupling components of the FOrrnula III there may be used accordingto the invention benzene or naphthalene compounds which couple in the orp-position to a primary, secondary or tertiary amino group. Suitableprimary amines are, for example, aniline, toluidines, xylidines,anisidines, phenylene diamines, toluylene diamines, amino cresol ethers,alkoxy anilines, chloroanilines, 3-acylamino anilines, dialkoxy anilinesor naphthyl amines. As secondary or tertiary amines there may be usedcompounds which contain as substituents in the amino group, lower alkylradicals, for example, methyl, ethyl, propyl or butyl radicals, aralkyl,cycloalkyl or aryl radicals which may contain one or more furthersubstituents, for exampe, halogen atoms, hydroxy, cyano, carbalkoxy,carbamyl, acyloxy, phenyl, alkoxy, phenoxy or dialkylamino groups. Inthe tertiary amines, R and R may form with each other or with a furthernitrogen atom or an oxygen atom, hydrogenated heterocycles, for example,the piperidine, morpholine or piperazine rings. The benzene or thenaphthalene radical A may contain one or more other substituents, forexample, halogen atoms, alkyl, alkoxy, carbalkoxy, alkyl-sulfone, cyanoor acylamino groups.

The monoazo dyestuffs of the Formula IV used in the method (b) can beprepared by methods known per se, for example by coupling the diazotizedamine of the Formula VI N'Hz Z (VI) with a coupling component of theFormula III or by alkaline condensation of an amine of the Formula VIwith the corresponding p-nitroso compound of a tertiary amine of thebenzene or the naphthalene series corresponding to Formula III.

The dyestuifs obtained according to the present invention contain as theanion X preferably the radical of a strong acid, for example, that ofsulfuric acid or of its semi-esters, of an arylsulfonic acid or of ahydrohalic acid. These anions, introduced according to the process ofthe present invention can also be replaced by anions of other acids, forexample, those of phosphoric acid, acetic acid, oxalic acid, lactic acidor tartaric acid. Furthermore, the dyestuffs can be obtained in form oftheir double salts with zinc or cadmium halides.

The new dyestuffs are suitable for the dyeing or printing of tannednatural or regenerated cellulose fibres, silk, leather or syntheticfibers, for example, acetate rayon, polyamide fibers or polyester fibersmodified by acids, especially fibers containing polyacrylonitrile orpolyvinylidene-cyanide. The dyeings produced on these fibers aregenerally very clear and very intense and generally have a good fastnessto light and to wetting.

The following examples illustrate the invention but they are notintended to limit it thereto, the parts being by weight unless mentionedotherwise.

EXAMPLE 1 A mixture of 3.75 parts of l-amino 2 acetylaminobenzene, 25parts of water and 2 parts of magnesium oxide was combined whilestirring at 50-60 C. with 12.6 parts of dimethyl sulfate, the whole wasstirred for 1 hour at this temperature, then cooled and filtered. 9parts of a sulfuric acid of 95% strength were added to the filtrate, themixture was heated at the boil for 1 hour and the solution of2-amino-phenyl-l-trimethylammonium methylsulfate thus obtained wascooled to 05 C. Subsequently, diazotization was effected with 5 parts byvolume of 5 N- sodium nitrite solution, the solution was stirred for 30minutes, the excess of nitrite was destroyed by means of amidosulfonicacid and the diazo solution was clarified by means of kieselguhr. 3.9parts of 3 chloro-N,N-dimethylaniline were added to the diazo solutionthus obtained and the whole was stirred for 2 hours at room temperature.The product was salted out with sodium sulfate the precipitated dyestuffof the formula was suction-filtered, washed with a sodium sulfatesolution of 14% strength and dried. There were obtained 8 parts of adyestuff which was easily soluble in water and dilute acetic acid whilegiving a yellow orange color.

4 grams of the dyestuff were stirred with 12 cc. of a 50%-acetic acidand the mixture was dissolved by pouring 200 cc. of hot water onto it.The stock solution was introduced into a dyeing apparatus forcross-wound bobbins which had been previously charged with 6 liters ofWater, 5 grams of crystallized sodium acetate and 50 grams of calcinedsodium sulfate. Then 400 grams of polyacrylonitrile yarn in the form ofa cross-wound bobbin were introduced and dyed under alternating liquorcirculation while slowly raising the temperature. From C. upwards thetemperature of the dyebath was only slowly raised to l06-108 C. and thenmaintained for 45 minutes. Thereafter, the dyebath was clearlyexhausted; it was cooled to about 70 C. and the dyeing was then treatedin usual manner. A clear gold-yellow dyeing having good fastness tolight and to wet processing was obtained.

When in the above example, instead of 3-chloro-N, N- dimethylaniline,the corresponding amount of 3-chloro-N- methyl-N-B-cyanoethyl-aniline or3 chloro-N-ethyl-N-pcyanoethyl-aniline was used and the proceduredescribed was followed, the dyestuffs of the formula ClIiCHzC N 2 wereobtained which dyed polyacryolnitrile fibers from an acetic acid bathorange tints having good fastness to light and wet processing.

EXAMPLE 2 A mixture of 4.6 parts of l-amino-Z-acetylamino-S-chlorobenzene, 25 parts of water and 2 parts of magnesium oxide wascombined while stirring at 50-60 C. with 12.6 parts of dimethyl sulfate,the mixture was stirred for 1 hour at this temperature, cooled andfiltered. 20 parts by volume of concentrated hydrochloric acid wereadded to the filtrate, the mixture was heated at the boil for 1 hour andthe solution of 5-chloro-2- aminophenyl-l trimethylammoniummethylsulfate thus obtained was cooled to 0-5 C. Diazotization waseffected with 5 parts by volume of a 5 N-sodium nitrate solution, thesolution was stirred for 30 minutes, the excess of nitrite was destroyedby means of amidosulfonic acid and the diazo solution was clarified bymeans of kieselguhr. 4.7 parts of3-methyl-N-ethyl-N-fl-cyanoethyl-aniline were added to the diazosolution thus obtained, the whole was stirred for 2 hours at roomtemperature and by adding parts by volume of zinc chloride lye having astrength of 70% the zinc chloride double salt of the dyestulf of theformula 6 We claim: 1. The water-soluble basic monoazo dyestufl of theformula 5 (EH; Y R CHz-N-CH; 4

| 9 2 a N=NAN e Q Q K 99 R N R X e cmcHzcN l0 2 Hz 2 it!) l :8 23 ;3 3:2g zii figgi gg figfi g gi f x g i in which Y represents hydrogen,chlorine, bromine. lowstuff were obtained which was easily soluble inwater and er alkyl lower g mfiuommethyl lower alkyl dilute acetic acidwhile giving a yellow-orange color. 9 i or reprefsfms g chlo- 1 gram ofthe dyestufl was stirred with 2.5 grams of {gai ii i g gvg gg f f a50%-acetic acid and the mixture was dissolved in 6 c g; alk l h 40W r i8 alko liters of water. 1 gram of crystallized sodium acetate and y y yr y e y 6 Ky 10 grams of calcined Sodium sulfate were also added loweralkyl, dimethyl-ammo-lower alkyl, carbamyl-lower to the dyebath.Subsequently 100 grams of p o1yacryl0 alkyl, carb-lower alkoxy-loweralkyl or benzyl, A reprenitrile staple fiber yarn that had beenpreviously washed Sems phepylene chlorophenylene lower alkyl'phenylenewere introduced into the dyebath having a temperature ofacetylammo'phegylene Garb-lower. alkoxy'phenylene or 60 C., thetemperature was slowly raised to 100 C. g i ii i g gg (1 t if f th anddyeing was elfected within 1 hour at boiling temperaforth 1 e w 50 e s cmom azo yes u o e ture. The dyebath was then allowed to cool slowly to70 a C., the goods were rinsed and dried. A clear orange dyeing wasobtained which had a good fastness to light and wet processing. H3

The following table indicates other dyestulfs which N=N -N 96 can beobtained according to the present invention, and 2 the tints of thedyeings produced with them on poly- CH:N-NCH: Cl 2 acrylonitrile fibers.i

Dyestuffs the cation of which corresponds to the general formula 3. Thewater-soluble basic monoazo dyestulf of the formula Y R N/ 5 6 4g1 N=NA*N S0496 E I CZHE T CHr N6B CH; I

l t: 45 AH! R1 R: R; Y Z R5 Tint yl.. MethyL. Hydrogen Hydrogen...N,N-dimethylanillne Orange.

do do (1 do Do.

Hydrogen. 5-methyl 0... D0 ..do do.

1410... 5-Inethylsulf0ny1.-...d

Hydrogen ..do -II 3-acetylamino-N.N-dimethylanlllne3-carbethoxy-N,N-diethylanlllne Orange.3-ch1oro-N,N-dl-B-hydroxyethylanlline Do.3-methyl-N-ethyl-Nfl-hydroxyethylanlllne Do. N.N-dibutylaniline go. o.N-(3qnethylphenyl)-morpholine Do. N-Z-ehlorophenyD-amino acetic acidethyl ester- Do.

2-chloro-N ethylaniline Yellow.

Z-chloro-N-fl-cyanoethylaniline Do. S-methyl-N,N-dlmethylanlllne. Orange...do D0.

. 3-chloro-N,N-dlrnethylanlline.. D0.

fl-chloro-N.N-dlethylanillue-- Bo.

o 0. Hydrogen. itchor o-N ,N-dlmethylaniline Orfin ge 8 4. Thewater-soluble basic monoazo dyestutf of the 6. The water-soluble basicmonoazo dyestulf f the formula formula /CH3 N=N =NHCHzCHz-0N 5 99 98CH2CH2CN ZnCh CH3N-CH1 c1 1 CHa-N-CH; C1 a) 10 References Cited UNITEDSTATES PATENTS 2 526 water-soluble bas1c monoazo dyestuff of the3,454,552 7/1969 Yamaya et all 260205 CHARLES B. PARKER, PrimaryExaminer C. F. WARREN, Assistant Examiner 1 l CII CHzCN sofi US. Cl.X.R.

